CN1377299A - Process for producing a metal aluminate catalyst support - Google Patents

Process for producing a metal aluminate catalyst support Download PDF

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Publication number
CN1377299A
CN1377299A CN00813697A CN00813697A CN1377299A CN 1377299 A CN1377299 A CN 1377299A CN 00813697 A CN00813697 A CN 00813697A CN 00813697 A CN00813697 A CN 00813697A CN 1377299 A CN1377299 A CN 1377299A
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Prior art keywords
alumina
component
metal
nitrate
catalyst support
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CN00813697A
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Chinese (zh)
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M·M·约翰森
T－T·P·成
D·B·提德克
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Phillips Petroleum Co
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Phillips Petroleum Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/023—Coating using molten compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/524—Spinel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

A process of making a metal aluminate catalyst support by incorporating, preferably impregnating, alumina, preferably gamma alumina, with a metal component to thereby provide a metal-incorporated alumina which is then calcined under a calcining condition to thereby provide a metal aluminate catalyst support. Such calcining condition includes a temperature in the range of from about 600 DEG C. to about 1350 DEG C. Preferably the metal component has been melted under a melting condition to thereby provide a melted metal component.

Description

Produce the method for metal aluminate catalyst support
Background of the present invention
The method that the present invention relates to metal aluminate catalyst support and produce this type of metal aluminate catalyst support.
Be known that catalyst,, can be used in the selection hydrogenation and the dehydrogenation of hydrocarbon as the zinc aluminate carrier with metal aluminate carrier.Generally speaking, the art methods of producing this type of metal aluminate carrier typically comprises the physical mixed metal component, as metal oxide, and al composition, as aluminium oxide, subsequent drying and calcining obtain containing the metal aluminate catalyst support of metal aluminate such as zinc aluminate, are also referred to as gahnite.Another commonsense method of producing this type of metal aluminate catalyst support comprises that subsequent drying and calcining are as disclosed method in US patent 3,641,182 with the aqueous solution and the al composition such as the aqueous solution of aluminum nitrate co-precipitation together of metal component such as metal nitrate.Yet these methods are expensive and consuming time.Therefore, the method that does not involve the production metal aluminate catalyst support of physical mixed or co-precipitation will all have important contribution to prior art with to economy.
General introduction of the present invention
Be desirable to provide a kind of method of producing metal aluminate catalyst support, it does not comprise the physical mixed of metal component and al composition.
Be desirable to provide a kind of method of producing metal aluminate catalyst support once more, it does not comprise the co-precipitation of metal component and al composition.
Be desirable to provide a kind of method of producing metal aluminate catalyst support again, it is more economical more worthwhile and easier than the method for prior art.
According to an aspect of the present invention, provide the method for producing metal aluminate catalyst support.These class methods comprise alumina are combined with metal component, preferably with motlten metal component dipping alumina, thereby obtain combining the alumina of metal, subsequent drying and high-temperature calcination, thus metal aluminate catalyst support is provided.This type of metal aluminate catalyst support contains metal aluminate, it with by physical mixed metal component (as metal oxide) and al composition (as aluminium oxide) or by the co-precipitation pregnant solution with to contain those metal aluminate catalyst supports that solution, subsequent drying and the calcining of aluminium produce similar.
According to a further aspect in the invention, provide by flooding alumina, the metal aluminate catalyst support that the method for subsequent drying and high-temperature calcination is prepared a kind of comprising with metal component (preferred molten metal component).
According to another aspect of the present invention, provide metal aluminate catalyst support.
Other purpose of the present invention and advantage will become clearer from detailed description of the present invention and claims.Detailed description of the present invention
Have been found that, metal aluminate catalyst support can be easily from existing preformed alumina (being also referred to as aluminium oxide) sheet stock, pellet, extrudate, round etc., and the preparation of their bond, this is by combining this type of alumina with metal component (preferred molten metal component), preferably use metal component (preferred molten metal component) dipping alumina, then dry and then high-temperature calcination realize.Formed metal aluminate catalyst support contains metal aluminate such as zinc aluminate, is also referred to as gahnite, and it is to form on the surface in the periphery of alumina easily.This type of metal aluminate catalyst support preparation is than comprising physical mixed metal component such as metal oxide and al composition such as aluminium oxide, or co-precipitation containing metal and contain the solution of aluminium, expand calcining subsequently and granulate then and/or to extrude the technology of preparing that forms catalyst ball or pellet more cheap and easy.
Usually, the alumina that is used for according to the inventive method production metal aluminate catalyst support disclosed herein can be any suitable alumina, for example, but is not limited to, alpha-aluminium oxide, βYang Hualv, δ alumina, the η alumina, γ alumina and similar alumina and their bond.Preferably, this type of alumina is the γ alumina.This alumina can also contain a spot of other composition, for example, the silica in about 1wt% silica arrives about 10wt% silica scope, this can influence the quality of metal aluminate catalyst support sharply.Usually, wish to have pure basically aluminium oxide, preferred pure basically γ alumina is as the parent material of preparation metal aluminate catalyst support.This initial alumina can prepare by any way well known in the prior art or method.As an example, the suitable initial alumina that is purchased that is used for preparing according to the inventive method disclosed herein metal aluminate catalyst support is γ alumina tablet or extrudate pellet or ball, those that make as the Engelhard Company by the UOP Inc. of Illinois McCook and Ohio Elyria.
The alumina that is suitable in the inventive method described here can be a feature to have following properties also.Usually, the surface area of alumina is at about 5m 2/ g (by Brunauer, Emmett, the Teller method, promptly the BET method is measured) to about 400m 2In/g the scope, preferably at about 10m 2/ g is to about 300m 2Between/the g, most preferably at 50m 2/ g to 200m 2Between/the g.
The pore volume of alumina normally at about 0.05ml/g between about 2ml/g, preferably at about 0.10ml/g extremely between about 1.5ml/g, with most preferably between 0.20ml/g to 1ml/g.
The average pore size of alumina normally at about 5 dusts between about 600 dusts, preferably at about 10 dusts between about 500 dusts, and most preferably between 25 dust to 200 dusts.
This alumina can have any suitable shape or form.Preferred this type of alumina is in the form of tablet, pellet, extrudate, ball etc. and their mixture and so on.This alumina has usually at about 0.5 millimeter (mm) between about 10mm, preferably at about 1mm extremely between about 8mm, and the granularity between 1mm to 6mm most preferably.
Any metal component that can form spinelle when using according to method disclosed herein can both use.Be used for metal with this type of metal component and be attached to alumina, be combined on the alumina or be incorporated in the alumina, preferably with the metal impregnation of this type of metal component to alumina, be immersed on the alumina or be impregnated in the alumina, and provide the example of a kind of potential suitable metal component of the alumina that combines metal to include but not limited to, the zinc component, magnesium component, calcium component, the barium component, the beryllium component, cobalt component, iron component, the manganese component, strontium component, lithium component, potassium component etc. and their mixture.Being used for metal with this type of metal component is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably with the metal impregnation of this type of metal component in alumina, be immersed on the alumina or be impregnated in the alumina, and provide the example of a kind of potential suitable metal component of the alumina that combines metal to include but not limited to, the zinc component, the magnesium component, the calcium component waits and their mixture.More preferably, this type of metal component is the zinc component.
Be used for zinc is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably holding zinc is impregnated in the alumina, is immersed on the alumina or the example that is impregnated into the potential suitable zinc component in the alumina comprises, but be not limited to, the zinc nitrate hexahydrate, zinc nitrate, the zinc nitrate of hydration, zinc chloride, zinc acetate dihydrate, zinc acetylacetone,2,4-pentanedione salt hydrate, zinc carbonate hydroxide monohydrate, the zinc perchlorate hexahydrate, the zinc sulfate of hydration, zinc sulfate monohydrate, zinc sulfate heptahydrate etc. and their bond.Be used for zinc is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into zinc in the alumina, be immersed on the alumina or zinc nitrate that to be impregnated into the preferred zinc component in the alumina be hydration.Be used for zinc is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into zinc in the alumina, be immersed on the alumina or the most preferably zinc component that is impregnated in the alumina is the zinc nitrate hexahydrate.
Be used for magnesium is attached to alumina, be combined on the alumina or be incorporated in the alumina, preferably magnesium is impregnated in the alumina, the example that is immersed on the alumina or is impregnated into the potential suitable magnesium component in the alumina comprises, but be not limited to, the magnesium nitrate hexahydrate, magnesium nitrate, the magnesium nitrate of hydration, magnesium chloride, the magnesium chloride of hydration, magnesium chloride hexahydrate, magnesium acetate 4 hydrate, magnesium acetylacetonate dihydrate, magnesium carbonate hydroxide pentahydrate, magnesium perchlorate, magnesium perchlorate hexahydrate, magnesium sulfate, magnesium sulfate 7 hydrate, magnesium sulfate monohydrate etc. and their bond.Be used for magnesium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into magnesium in the alumina, be immersed on the alumina or the preferably magnesium component that is impregnated in the alumina is the magnesium nitrate of hydration.Be used for magnesium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into magnesium in the alumina, be immersed on the alumina or the most preferably magnesium component that is impregnated in the alumina is the magnesium nitrate hexahydrate.
Be used for calcium is attached to alumina, be combined on the alumina or be incorporated in the alumina, preferably calcium is impregnated in the alumina, the example that is immersed on the alumina or is impregnated into the potential suitable calcium component in the alumina comprises, but be not limited to, calcium nitrate tetrahydrate, calcium nitrate, the calcium nitrate of hydration, calcium chloride, the calcium chloride of hydration, calcium chloride dihydrate, the calcium chloride hexahydrate, calcium chloride hydrate, the calcium acetate hydrate, the calcium acetate monohydrate, calcium acetylacetone,2,4-pentanedione salt hydrate, the Calcium perchlorate tetrahydrate, calcium sulfate, calcium sulfate dihydrate, calcium sulfate hemihydrates etc. and their bond are used for calcium is attached to alumina, be combined on the alumina or be incorporated in the alumina, preferably calcium is impregnated in the alumina, be immersed on the alumina or calcium nitrate that to be impregnated into the preferred calcium component in the alumina be hydration is used for calcium is attached to alumina, be combined on the alumina or be incorporated in the alumina, preferably calcium is impregnated in the alumina, the most preferably calcium component that is immersed on the alumina or is impregnated in the alumina is a calcium nitrate tetrahydrate.
Be used for barium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into barium in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable barium component in the alumina includes, but are not limited to, barium nitrate, the barium nitrate of hydration, barium chloride, the barium chloride of hydration, barium chloride dihydrate, barium acetate, barium acetylacetone,2,4-pentanedione salt hydrate, brium carbonate, barium perchlorate, barium perchlorate trihydrate, barium sulfate etc. and their bond.Be used for barium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into barium in the alumina, be immersed on the alumina or barium nitrate that to be impregnated into the preferred barium component in the alumina be hydration.Be used for barium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into barium in the alumina, be immersed on the alumina or the most preferably barium component that is impregnated in the alumina is a barium nitrate.
Be used for beryllium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into beryllium in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable beryllium component in the alumina comprises, but be not limited to, the beryllium nitrate trihydrate, the beryllium nitrate of hydration, beryllium chloride, the beryllium sulfate of hydration, beryllium sulfate tetrahydrate etc. and their bond.Be used for beryllium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into beryllium in the alumina, be immersed on the alumina or beryllium nitrate that to be impregnated into the preferred beryllium component in the alumina be hydration.Be used for beryllium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into beryllium in the alumina, be immersed on the alumina or the most preferably beryllium component that is impregnated in the alumina is the beryllium nitrate trihydrate.
Be used for cobalt is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into cobalt in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable cobalt component in the alumina comprises, but be not limited to, Cobalt(II) nitrate hexahydrate, the cobalt nitrate of hydration, cobalt chloride, the cobalt chloride of hydration, cobalt chloride hexahydrate, the cobalt chloride hydrate, cobalt acetate tetrahydrate, cobalt acetylacetonate, cobalt acetylacetone,2,4-pentanedione salt hydrate, the cobalt carbonate hydrate, cobaltous perchlorate hexahydrate, the cobaltous sulfate of hydration, cobaltous sulfate hydrate etc. and their bond.Be used for cobalt is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into cobalt in the alumina, be immersed on the alumina or cobalt nitrate that to be impregnated into the preferred cobalt component in the alumina be hydration.Be used for cobalt is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into cobalt in the alumina, be immersed on the alumina or the most preferably cobalt component that is impregnated in the alumina is a Cobalt(II) nitrate hexahydrate.
Be used for iron is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into iron in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable iron component in the alumina includes, but are not limited to, the ferric nitrate nonahydrate, the ferric nitrate of hydration, iron chloride, the iron chloride of hydration, the iron chloride tetrahydrate, ferric chloride hexahydrate, ferric acetate, the iron acetylacetonate, ferric perchlorate's hexahydrate, the ferric sulfate of hydration, ferric sulfate heptahydrate etc. and their bond.Be used for iron is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into iron in the alumina, be immersed on the alumina or ferric nitrate that to be impregnated into the preferred iron component in the alumina be hydration.Be used for iron is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into iron in the alumina, be immersed on the alumina or the most preferably iron component that is impregnated in the alumina is the ferric nitrate nonahydrate.
Be used for manganese is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into manganese in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable manganese component in the alumina comprises, but be not limited to, the manganese nitrate hexahydrate, the manganese nitrate of hydration, the manganese nitrate hydrate, manganese chloride, the manganese chloride of hydration, the manganese chloride tetrahydrate, the manganese acetate dihydrate, manganese acetate tetrahydrate, manganese acetylacetonate, manganese carbonate, perchloric acid manganese hexahydrate, the manganese sulfate of hydration, manganese sulfate monohydrate etc. and their bond.Be used for manganese is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into manganese in the alumina, be immersed on the alumina or manganese nitrate that to be impregnated into the preferred manganese component in the alumina be hydration.Be used for manganese is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into manganese in the alumina, be immersed on the alumina or the most preferably manganese component that is impregnated in the alumina is the manganese nitrate hexahydrate.
Be used for strontium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into strontium in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable strontium component in the alumina includes, but are not limited to, strontium nitrate, the strontium nitrate of hydration, strontium chloride, the strontium chloride of hydration, the strontium chloride hexahydrate, strontium acetate, strontium acetylacetonate, strontium carbonate, perchloric acid strontium hydrate, the strontium sulfate of hydration, strontium sulfate etc. and their bond.Be used for strontium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into strontium in the alumina, be immersed on the alumina or the preferred strontium component that is impregnated in the alumina is a strontium nitrate.
Be used for lithium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into lithium in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable lithium component in the alumina includes, but are not limited to, lithium nitrate, the lithium nitrate of hydration, lithium chloride, the lithium chloride of hydration, the lithium chloride hydrate, lithium acetate dihydrate, lithium acetylacetonate, lithium perchlorate, lithium perchlorate trihydrate, lithium sulfate, lithium sulfate monohydrate etc. and their bond.Be used for lithium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into lithium in the alumina, be immersed on the alumina or the preferred lithium component that is impregnated in the alumina is a lithium nitrate.
Be used for potassium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into potassium in the alumina, be immersed on the alumina or the example that is impregnated into the potential suitable potassium component in the alumina comprises, but be not limited to potassium nitrate, the potassium nitrate of hydration, potassium chloride, the potassium chloride of hydration, potassium acetylacetonate semihydrate, potash sesquialter hydrate, potassium hyperchlorate, potassium sulfate etc. and their bond.Be used for potassium is attached to alumina, is combined on the alumina or is incorporated in the alumina, preferably be impregnated into potassium in the alumina, be immersed on the alumina or the preferred potassium component that is impregnated in the alumina is a potassium nitrate.
By utilizing metal with this type of metal component to be attached in the base material (as alumina), to be combined on the base material or to be incorporated into base material, cause forming alumina in conjunction with metal, dry then and calcining obtains any suitable method or the method for metal aluminate catalyst support, and this metal component is attached in the alumina, is combined on the alumina or is incorporated in the alumina.In conjunction with the mode or the example of method include, but not limited to dipping, soak, spraying waits and their combination.In conjunction with method for optimizing be to use by any standard incipient wetness dipping technique of metal component dipping alumina base material (promptly using this) and flood in conjunction with the solution of the element hole of complete filling base material basically.Preferable methods uses dipping solution, the latter to comprise the metal component of desired concn so that finally provide and combine metal, and the alumina of preferred impregnating metal can carry out drying and high-temperature calcination then, produces metal aluminate catalyst support.
Also wish to use the aqueous solution of metal component with the dipping alumina.Preferred dipping solution comprises that (preferably this type of metal component presents metallic salt form by metal component, for example, but be not limited to metal chloride, metal nitrate, metal sulfate etc. and their mixture) be dissolved in solvent (as, however be not limited to water, alcohols, ester class, ether, ketone etc. and their mixture) in the formed aqueous solution.
Preferred dipping solution be by with metal component (as the zinc nitrate hexahydrate, magnesium nitrate hexahydrate, calcium nitrate tetrahydrate, barium nitrate, the beryllium nitrate trihydrate, Cobalt(II) nitrate hexahydrate, ferric nitrate nonahydrate, the manganese nitrate hexahydrate, strontium nitrate, lithium nitrate, potassium nitrate, preferably, zinc nitrate hexahydrate) be dissolved in the water formed.Acceptable is to use some acid solutions to assist the dissolving of metal component.Preferably, contain the hexahydrated aqueous solution of zinc nitrate soluble in water, with zinc component dipping alumina by use.In addition, magnesium nitrate hexahydrate or calcium nitrate tetrahydrate or barium nitrate or beryllium nitrate trihydrate or Cobalt(II) nitrate hexahydrate or ferric nitrate nonahydrate or manganese nitrate hexahydrate or strontium nitrate or lithium nitrate or potassium nitrate can be used for replacing the zinc nitrate hexahydrate, so that with the metal impregnation alumina of each metal component.
The metal of metal component is attached in the alumina, is combined on the alumina or the more preferably method in the alumina of being incorporated into is to flood this type of alumina with molten metal component under the described melting condition here.Preferred this type of metal component presents the form of slaine, for example, but is not limited to metal chloride, metal nitrate, metal sulfate and their bond (as, but be not limited to the zinc nitrate hexahydrate, the magnesium nitrate hexahydrate, calcium nitrate tetrahydrate, barium nitrate, the beryllium nitrate trihydrate, Cobalt(II) nitrate hexahydrate, ferric nitrate nonahydrate, the manganese nitrate hexahydrate, strontium nitrate, lithium nitrate, potassium nitrate etc. and their bond, preferred, the zinc nitrate hexahydrate).The interpolation in metal component of a spot of water-bearing media such as water can be used in the fusing of assisting this type of metal component.
This type of melting condition comprises: than the low temperature of the decomposition temperature of metal component, time and pressure are enough to provide the molten metal component, preferred dumpable deposite metal component.This term decomposition temperature " be meant a kind of like this temperature, under this temperature metal component no longer dissolve and no longer be fit to the metal of this type of metal component in conjunction with (preferred dipping) in alumina, on alumina or go in the alumina.This term " dumpable motlten metal component " is meant the metal component that is under the melting condition and has enough viscosity to be toppled over.
The temperature lower than the decomposition temperature of metal component will change according to the difference of metal component, but this temperature should be enough to provide the melt metal component.This temperature is normally between about 25 ℃ to about 160 ℃, preferably between about 30 ℃ to about 150 ℃, more preferably between about 35 ℃ to about 140 ℃, most preferably between 35 ℃ to 130 ℃.
This melting condition can comprise usually between about 1 minute to about 2 hours, preferably between about 5 minutes to about 1.5 hours, and time between 5 minutes to 1 hour most preferably.This melting condition can comprise usually in about atmospheric pressure (being that about 101.2kPa arrives about 150 absolute per square inch poundages (pound/square inch) to about 1033kPa (about 14.7 absolute per square inch poundage)) scope, preferably at about 101.2kPa in about 689kPa (about atmosphere is pressed onto about 100 pounds/square inch) scope, most preferably from about atmospheric a kind of pressure is as long as desired temperature can keep.
So the molten metal component is used for this type of deposite metal component in conjunction with (preferred dipping) then to alumina, on alumina or go in the alumina.Utilization can make whole basically surface area of alumina scribble any way or the method for deposite metal component, by on the surface that this type of deposite metal component is poured over alumina this type of molten metal component being joined in the alumina, with the metal of this type of deposite metal component in conjunction with (preferred dipping) in alumina, on alumina or go in the alumina.Preferably, this type of deposite metal component is poured onto on the surface of alumina, and meanwhile alumina is under the constant stirring or rollover states.
Also wished before the deposite metal component is poured onto on the surface of alumina this alumina of preheating under heating condition.This heating condition is usually included between about 80 ℃ to about 150 ℃, preferably between about 85 ℃ to about 140 ℃, and the temperature between about 90 ℃ to about 130 ℃ most preferably.This heating condition can comprise usually between about 1 minute to about 2 hours, preferably between about 5 minutes to about 1.5 hours, and time between 5 minutes to 1 hour most preferably.This heating condition can comprise usually in the extremely about 1033kPa of about 101.2kPa (about atmospheric pressure (promptly about 14.7 absolute per square inch poundage) is to about 150 absolute per square inch poundages (pound/square inch)) scope, preferably at about 101.2kPa in about 689kPa (about atmosphere is pressed onto about 100 pounds/square inch) scope, most preferably from about atmospheric a kind of pressure is as long as desired temperature can keep.Combine the alumina of metal (preferably having flooded metal) can be further near one section of the temperature heating of the fusing point of metal component between about 0.5 hour to about 15 hours, preferably between about 1 hour to about 8 hours, time between 1 hour to 5 hours most preferably.
In most preferred method, the zinc nitrate hexahydrate of fusing is used for the hexahydrated zinc of this type of fusing zinc nitrate in conjunction with (preferred dipping) to alumina, on alumina or go in the alumina.Utilization can make whole basically surface area of alumina scribble fusing hexahydrated any way of zinc nitrate or method, be poured on the surface of alumina the zinc nitrate hexahydrate of this fusing joined in the alumina by melting the zinc nitrate hexahydrate, should melt the hexahydrated zinc of zinc nitrate in conjunction with (preferred dipping) in alumina, on alumina or go in the alumina.Preferably, this fusing zinc nitrate hexahydrate is poured onto on the surface of alumina, and meanwhile alumina is under the constant stirring or rollover states.In addition, magnesium nitrate hexahydrate or calcium nitrate tetrahydrate or barium nitrate or beryllium nitrate trihydrate or Cobalt(II) nitrate hexahydrate or ferric nitrate nonahydrate or manganese nitrate hexahydrate or strontium nitrate or lithium nitrate or potassium nitrate can replace the zinc nitrate hexahydrate to be used for the metal of this type of metal component in conjunction with (preferred dipping) to alumina, on alumina or go in the alumina, according to the above same way as that is used to combine (preferably flooding) the hexahydrated zinc of zinc nitrate.
Usually, combined (preferred dipping) in alumina, in alumina or the amount of going into the metal component (preferred zinc component) in the alumina be a kind of like this amount, the alumina that combines metal has carried out drying and calcining according to the inventive method disclosed herein after, this amount is enough to provide metal aluminate catalyst support, and the latter has generally at about 1wt% to the metal aluminate amount between about 100wt% (with respect to the gross weight of metal aluminate catalyst support).Preferably, the amount of metal is the amount that metal aluminate catalyst support can be provided in combining the alumina of metal, this carrier have with respect to about 15wt% of metal aluminate catalyst support gross weight between about 75wt%, the amount of the metal aluminate between 25wt% to 65wt% most preferably.
The alumina that combines metal is dry under drying condition then.Usually, this drying condition is included between about 80 ℃ to about 140 ℃, preferably between about 90 ℃ to about 130 ℃, and the temperature between about 100 ℃ to about 120 ℃ most preferably.This drying condition can comprise that also being used for dry this combines the time of the alumina of metal, generally between about 0.5 hour to about 60 hours, preferably between about 1 hour to about 40 hours, most preferably between 1.5 hours to 20 hours, to produce the dry alumina that combines metal.This drying condition also can comprise usually in the extremely about 1033kPa of about 101.2kPa (about atmospheric pressure (promptly about 14.7 absolute per square inch poundage) is to about 150 absolute per square inch poundages (pound/square inch)) scope, preferably at about 101.2kPa in about 689kPa (about atmosphere is pressed onto about 100 pounds/square inch) scope, most preferably from about atmospheric a kind of pressure is as long as desired temperature can keep.Known any seasoning in the prior art field, as air-dry, heat drying etc. and their combination can both be used.
The so dry alumina that combines metal is calcined under calcination condition then, obtains metal aluminate catalyst support in view of the above.This calcination condition for provide the physical property that has in the disclosed here scope for example the metal aluminate catalyst support of surface area, pore volume, average pore size and crystal farmland size be important, be fit to use the carrier of this metal aluminate catalyst support as hydrogenation and dehydrogenation.
Usually, this calcination condition can be included between about 600 ℃ to about 1350 ℃, preferably between about 675 ℃ to about 1300 ℃, and more preferably between about 800 ℃ to about 1250 ℃, the temperature between 900 ℃ to 1200 ℃ most preferably.This type of calcination condition can also comprise: usually at about 42.2kPa between about 5167kPa (about 7 absolute per square inch poundages (pound/square inch) arrive about 750 pounds/square inch), preferably at about 48.22kPa between about 3100kPa (about 7 pounds/square inch to about 450 pounds/square inch), most preferably at the pressure of about 48.2kPa between about 1033kPa (7 pounds/square inch to 150 pounds/square inch), and between about 1 hour to about 60 hours, preferably between about 2 hours to about 20 hours, time between 3 hours to 15 hours most preferably.
After the calcining that drying is crossed in conjunction with the alumina of metal, will be in alumina, obtain metal aluminate catalyst support of the present invention forming metal aluminate on the outer surface of alumina or on (but being not limited to) surface at alumina.The example of suitable metal aluminate includes, but are not limited to zinc aluminate, is also referred to as gahnite, magnesium aluminate, be also referred to as magnesia spinel, calcium aluminate is also referred to as the calcium spinelle, barium aluminate, be also referred to as the barium spinelle, beryllium aluminate is also referred to as Chrysoberyl, cobalt aluminate, be also referred to as cobalt spinel, iron aluminate could is also referred to as hercynite, manganese aluminate, be also referred to as galaxite, strontium aluminate is also referred to as the strontium spinelle, lithium aluminate, be also referred to as lithium-spinel, potassium aluminate is also referred to as the potassium spinelle, and their mixture.Preferred metal aluminate is to be selected from zinc aluminate, is also referred to as gahnite, and magnesium aluminate is also referred to as magnesia spinel, and calcium aluminate is also referred to as the calcium spinelle, and their mixture.Preferred metal aluminate is a zinc aluminate, is also referred to as gahnite.
The amount of the metal aluminate of metal aluminate catalyst support (preferred zinc aluminate catalyst carrier) generally is with respect to about 1wt% of the gross weight of metal aluminate catalyst support extremely between about 100wt%.Preferably, the amount of the metal aluminate of metal aluminate catalyst support of the present invention be with respect to about 15wt% of the gross weight of metal aluminate catalyst support between about 75wt%, most preferably between 25wt% to 65wt%.
The amount of the alpha-aluminium oxide of metal aluminate catalyst support (preferred zinc aluminate catalyst carrier) is normally at about 0wt% (based on the gross weight of metal aluminate catalyst support) extremely between about 99wt%, preferably at about 10wt% between about 85wt%, most preferably between 15wt% to 70wt%.The crystal farmland size of the alpha-aluminium oxide of metal aluminate catalyst support normally at about 25 dusts between about 3000 dusts, preferably at about 25 dusts between about 2500 dusts, and most preferably between 50 dust to 2000 dusts." crystal farmland size " is to measure from the spectral line broadening of X-ray diffraction spectral line.
The amount of the gamma-alumina of metal aluminate catalyst support (preferred zinc aluminate catalyst carrier) is normally at about 0wt% (based on the gross weight of metal aluminate catalyst support) extremely between about 60wt%, preferably at about 0wt% between about 50wt%, most preferably between 0wt% to 40wt%.
The surface area of metal aluminate catalyst support (preferred zinc aluminate catalyst carrier) is normally at about 1m 2/ g (by Brunauer, Emmett, the Teller method, promptly the BET method is measured) to about 200m 2Between/the g, preferably at about 1m 2/ g is to about 150m 2Between/the g, more preferably at about 5m 2/ g is to about 125m 2Between/the g, most preferably at 10m 2/ g to 80m 2Between/the g.
The pore volume of metal aluminate catalyst support (preferred zinc aluminate catalyst carrier) normally at about 0.05ml/g between about 2ml/g, preferably at about 0.10ml/g extremely between about 1.5ml/g, with most preferably between 0.10ml/g to 1ml/g.
The average pore size of metal aluminate catalyst support (zinc aluminate catalyst carrier) normally at about 50 dusts between about 1000 dusts, preferably at about 50 dusts between about 750 dusts, most preferably between 50 dust to 450 dusts.
The crystal farmland size of the metal aluminate of metal aluminate catalyst support (preferred zinc aluminate) normally at about 25 dusts between about 1750 dusts, preferably at about 25 dusts between about 1500 dusts, more preferably at about 25 dusts between about 1250 dusts, and most preferably between 25 dust to 1000 dusts.
The granularity of metal aluminate catalyst support (preferred zinc aluminate catalyst carrier) generally is between about 10mm, preferably at about 1mm extremely between about 8mm, most preferably between 1mm to 6mm at about 0.5 millimeter (mm).
By the metal aluminate catalyst support that the inventive method described here makes, preferred zinc aluminate catalyst carrier can be used as in for example US patent 5,510,550; US patent 5,475,173; With the catalyst carrier in the selective hydrogenation process of describing in the US patent 5,583,274.The metal aluminate catalyst support that is made by the inventive method described here, preferred zinc aluminate catalyst carrier can be as the catalyst carrier in the process of describing in the US patent 3,641,182 for example in certain embodiments.
The following examples are in order to further specify the present invention, but needn't think restriction exceedingly this
Scope of invention.
Example I
This embodiment illustrates the preparation of various zinc aluminate catalyst carriers.
Carrier A (contrast) is by UOP Inc., McCook, the commodity γ alumina that Illinois provides obtains as the precalcining sheet stock with about 1/8 inch diameter, and it was calcined about 5 hours in air under about 900 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch).
Carrier B (contrast) is by UOP Inc., McCook, the commodity γ alumina that Illinois provides obtains as the precalcining sheet stock with about 1/8 inch diameter, and it was calcined about 4 hours in air under about 1100 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch).
Support C (the present invention) be prepared as follows.The γ alumina (by Englehard Company, Elyria, Ohio provides, and obtains as the screw form with about 1/8 inch diameter) that is purchased of 75.6g consumption was placed about 1 hour in 120 ℃ drying oven.The γ alumina that so heated is used about 66.9g zinc nitrate hexahydrate (Zn (NO then 3) 26H 2O) dipping, the latter was melted about 1 hour in drying oven under about 120 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch).By using the 5mL pipette, will melt the zinc nitrate hexahydrate and be added drop-wise to through 30 minutes and carry out γ alumina rotational circle spheroid in the γ alumina rotational circle spheroid with melting the hexahydrated dip operation of zinc nitrate.In the hexahydrated interpolation process of fusing zinc nitrate, continuous stirring γ alumina rotational circle spheroid material.When finishing, the alumina that combines zinc is placed a whole night in 120 ℃ drying oven (about 16 hours).The alumina of then drying being crossed that combines zinc is put into quartzy calcining tube, and temperature slowly is elevated to 110 ℃ and 110 ℃ of times that keep down 1 hour.In calcination process, constantly purge calcining tube with air.This temperature is lifted to 300 ℃ and kept 3 hours down at 300 ℃ then, observes NOx gas and overflow when being higher than 250 ℃.This temperature is increased to 350 ℃ and keep a whole night (about 16 hours) at 350 ℃, is increased to 500 ℃ and kept nine hours at 500 ℃ then.Allow calcining tube cool off about 48 hours, then temperature is increased to 120 ℃ and keep a whole night (about 16 hours) at 120 ℃.This temperature is enhanced 500 ℃ and kept 5 hours at 500 ℃ then.This temperature is enhanced 600 ℃ and kept 1.5 hours at 600 ℃ then.Then this calcining tube is cooled off about 2 hours time, the zinc aluminate catalyst carrier is provided.
Carrier D (the present invention) is according to preparing with the same mode of the above support C of the present invention, exception be, improving temperature to 600 ℃ and after 600 ℃ keep 1.5 hours down, temperature is increased to 700 ℃ and kept 1 hour down at 700 ℃.Then this calcining tube is cooled off about 2 hours time, the zinc aluminate catalyst carrier is provided.
Carrier E (the present invention) is according to preparing with the same mode of the above carrier D of the present invention, exception be, improving temperature to 700 ℃ and after 700 ℃ keep 1 hour down, temperature is increased to 820 ℃ and kept 1.5 hours down at 820 ℃.Then this calcining tube is cooled off about 2 hours time, the zinc aluminate catalyst carrier is provided.
Carrier F (the present invention) is following making.The γ alumina (by UOP Inc., McCook, Illinois provides, and obtains as the precalcining sheet stock form with about 1/8 inch diameter) that is purchased of 20g consumption was placed about 1 hour in 120 ℃ drying oven.The γ alumina that so heated is used about 33g zinc nitrate hexahydrate (Zn (NO then 3) 26H 2O) dipping, the latter was melted about 30 minutes under about 120 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch).By using the 5mL pipette, will melt the zinc nitrate hexahydrate and be added drop-wise to through 30 minutes and carry out the gamma-alumina pellet in the gamma-alumina pellet with melting the hexahydrated dip operation of zinc nitrate.In the hexahydrated interpolation process of fusing zinc nitrate, continuous stirring gamma-alumina pellet.When finishing, will in 120 ℃ drying oven, place about 15 hours in conjunction with the alumina of zinc.The alumina that combines zinc that drying like this is crossed is put into quartzy calcining tube and was calcined about 5 hours at air under 900 ℃ under the pressure of about atmospheric pressure (being about 14.7 pounds/square inch) then.Then this calcining tube is cooled off about 2 hours time, the zinc aluminate catalyst carrier is provided.
Carrier G (the present invention) is according to making with the same mode of above-described carrier F of the present invention, exception be that calcining is to carry out about 4 hours under about 1100 ℃ temperature, rather than carries out under about 900 ℃ calcining heat about 5 hours.
Carrier H (the present invention) is prepared as follows.The γ alumina (by Englehard Company, Elyria, Ohio provides, and obtains as the precalcining sheet stock form with about 1/8 inch diameter) that is purchased of 150g consumption was placed about 1 hour in 130 ℃ drying oven.The γ alumina that so heated is used about 136g zinc nitrate hexahydrate (Zn (NO then 3) 26H 2O) dipping, the latter was melted about 1 hour in drying oven under about 130 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch).By using the 5mL pipette, will melt the zinc nitrate hexahydrate and be added drop-wise to through 30 minutes and carry out the gamma-alumina pellet in the gamma-alumina pellet with melting the hexahydrated dip operation of zinc nitrate.In the hexahydrated interpolation process of fusing zinc nitrate, continuous stirring gamma-alumina pellet.When finishing, will in 130 ℃ drying oven, place about 48 hours in conjunction with the alumina of zinc.Then the so dry alumina of crossing in conjunction with zinc is put into quartzy calcining tube, the time through 3 hours under air purge is increased to 300 ℃ lentamente with temperature, observes NOx gas and overflows.In calcination process, constantly purge calcining tube with air.This temperature kept 3 hours down at 300 ℃, was increased to 400 ℃ then.These 400 ℃ of temperature are held a whole night (about 16 hours), are increased to 1100 ℃ through 2 hours then, keep 7 hours down at 1100 ℃ then.For providing the stove of heat, calcining tube closes a whole night then (about 16 hours).This calcining tube was heated to 1100 ℃ through 3 hours then, kept 4 hours down at 1100 ℃ then.Then this calcining tube is cooled off about 2 hours time, the zinc aluminate catalyst carrier is provided.
Carrier I (the present invention) is prepared as follows.The γ alumina (by Englehard Company, Elyria, Ohio provides, and obtains as the precalcining extrudate form with about 1/20 inch diameter) that is purchased of 75g consumption was placed about 1 hour in 120 ℃ drying oven.The γ alumina that so heated is used about 69.3g zinc nitrate hexahydrate (Zn (NO then 3) 26H 2O) dipping, the latter was melted about 2 hours in drying oven under about 130 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch).By using the 5mL pipette, will melt the zinc nitrate hexahydrate and be added drop-wise to through 30 minutes and carry out the gamma-alumina pellet in the gamma-alumina pellet with melting the hexahydrated dip operation of zinc nitrate.In the hexahydrated interpolation process of fusing zinc nitrate, continuous stirring gamma-alumina pellet.When finishing, will in 130 ℃ drying oven, place about 48 hours in conjunction with the alumina of zinc.Then the so dry alumina of crossing in conjunction with zinc is put into quartzy calcining tube, the time through 3 hours under air purge is increased to 350 ℃ lentamente with temperature, overflows at about NOx gas of observing more than 250 ℃.In calcination process, constantly purge calcining tube with air.Temperature keeps a whole night (about 16 hours) down at 350 ℃, is increased to 1100 ℃ through 3 hours then, keeps 6 hours down at 1100 ℃ then.Then this calcining tube is cooled off about 2 hours time, the zinc aluminate catalyst carrier is provided.
Carrier J (the present invention) is according to preparing with the same mode of above-described carrier I of the present invention, exception be that the dry alumina of crossing in conjunction with zinc is being used H under about 1100 ℃ temperature 2The air that O is saturated (is H 2The O flow velocity is the steam atmosphere of 20mL/hr) the middle processing about 4 hours, replace the heating under air purge.
From the physical characteristic of analyzing, as carrier A, B, C, D, E, F, G, H, the surface area of I and J, pore volume, average pore size and crystal farmland size are all listed in the Table I." crystal farmland size " is to measure from the spectral line broadening of X-ray diffraction spectral line.In addition, this X-ray diffraction spectral line has confirmed support C, D, and E, F, G, H, I and J respectively have zinc aluminate structure.
Table I
Carrier Calcining heat (℃) Surface area (m 2/g) Pore volume (mL/g) Average pore size (ang.) Zinc aluminate (ZnOAl 2O 3) CDS(ang.) α-Al 2O 3CDS(ang.) δ-Al 2O 3CDS(ang.) θ-Al 2O 3CDS(ang.) γ-Al 2O 3CDS(ang.)
A (contrast) 900 116 0.880 305 ND ND ND 95 60
B (contrast) 1100 33 0.479 581 ND 680 ND 215 ND
C (the present invention) 600 163 0.706 172 35 ND ND 55 ND
D (the present invention) 700 141 0.638 181 50 ND ND 55 ND
E (the present invention) 820 128 0.696 217 65 ND ND 65 ND
F (the present invention) 900 88 0.665 305 105 ND 110 ND 60
G (the present invention) 1100 25 0.284 446 225 740 185 ND ND
H (the present invention) 1100 14 0.145 401 1075 465 ND ND ND
I (the present invention) 1100 15 0.005 298 1295 335 ND ND ND
J (the present invention) 1100 (steam) 53 0.533 395 100 ＞2000 150 300 ND
CDS=crystal farmland size ang.=dust ND=undetermined
Data declaration in the Table I, the inventive method described here can be used in produces metal aluminate catalyst support such as zinc aluminate catalyst carrier.In addition, carrier G of the present invention, H and I demonstrate a surface area key factor of catalyst carrier for hydrgenating (make) of remarkable minimizing, with control vector Comparatively speaking.In addition, the data declaration in Table I is lower than about 1100 ℃ temperature lower calcination and will obtains the zinc aluminate catalyst carrier, and the surface area that the latter has is higher than the surface area when calcining under about 1100 ℃ according to the inventive method disclosed herein.
Example II
This embodiment has illustrated the preparation of several magnesium aluminate catalyst carriers and calcium aluminate catalyst carrier.
Carrier K (the present invention) is prepared as follows.The γ alumina (by LaRocheIndustries Inc., Atlanta, Georgia provides, and obtains as the precalcining sheet stock form with about 1/8 inch diameter) that is purchased of 90g consumption was placed about 30 minutes in 120 ℃ drying oven.The γ alumina that heated is used the magnesium nitrate hexahydrate (Mg (NO of about 45g then 3) 26H 2O) dipping, it melted about 30 minutes in drying oven under about 120 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch) after the deionized water that adds 20g.By using the 5mL pipette, fusing magnesium nitrate hexahydrate was added drop-wise to through 30 minutes carries out the dip operation of γ alumina sheet stock in the γ alumina sheet stock with the fusing magnesium nitrate.In the hexahydrated interpolation process of fusing magnesium nitrate, continuous stirring γ alumina sheet stock.This fusing magnesium nitrate hexahydrate dipping solution begins to solidify in the process that this magnesium nitrate hexahydrate is joined in the γ alumina sheet stock, approximately the magnesium nitrate solution of fusing is put back in the drying oven again in per 10 minutes in the whole 30 minutes process of this γ alumina sheet stock of dipping and heats about 3 minutes time under 120 ℃ again.
When finishing, the alumina that combines magnesium is placed a whole night in 120 ℃ drying oven (about 16 hours).Then the so dry alumina of crossing in conjunction with magnesium is put into quartzy calcining tube, the time through 3 hours under air purge is increased to 210 ℃ lentamente with temperature.This temperature is enhanced 320 ℃ and kept 3 hours down at 320 ℃ then.This temperature is enhanced 360 ℃ and kept 3 hours down at 360 ℃ then.This temperature is enhanced 400 ℃ and kept 14.5 hours down at 400 ℃ then.This temperature is enhanced 500 ℃ and kept 2 hours at 500 ℃ then.This temperature is enhanced 600 ℃ and kept 0.5 hour at 600 ℃ then.In heating process, do not observe NOx gas and overflow.
Calcining tube cools off a whole night (about 16 hours) then.Alumina in conjunction with magnesium is transferred to porcelain crucible then, and is following according to the Programmed Temperature Ramp degree temperature that raises.This temperature is increased to 150 ℃ through about 0.2 hour time, keeps about 1 hour down at 150 ℃ then.This temperature is increased to 300 ℃ through about 0.5 hour time then, keeps about 5 hours a period of time down at 300 ℃ then.This temperature is increased to 500 ℃ through about 1.7 hours time then, keeps about 5 hours a period of time down at 500 ℃ then.This temperature is increased to 775 ℃ through about 2.3 hours time then, keeps about 4 hours a period of time down at 775 ℃ then.This temperature is increased to 825 ℃ through about 0.8 hour time then, keeps about 4 hours a period of time down at 825 ℃ then.This temperature is increased to 875 ℃ through about 0.8 hour time then, keeps about 6 hours a period of time down at 875 ℃ then.This temperature is increased to 925 ℃ through about 0.8 hour time then, keeps about 4 hours a period of time down at 925 ℃ then.This temperature is increased to 1130 ℃ through about 0.7 hour time then, keeps about 10 hours a period of time down at 1130 ℃ then.Then porcelain crucible is cooled off about 2 hours time, the magnesium aluminate catalyst carrier is provided.
For the given temperature of Programmed Temperature Ramp is the temperature of program.The actual temperature that is reached is lower than program temperature slightly, and is as follows:
150 ℃ of degree design temperature=148 ℃ actual temperatures;
300 ℃ of degree design temperature=296 ℃ actual temperatures;
500 ℃ of degree design temperature=494 ℃ actual temperatures;
775 ℃ of degree design temperature=758 ℃ actual temperatures;
825 ℃ of degree design temperature=805 ℃ actual temperatures;
875 ℃ of degree design temperature=854 ℃ actual temperatures;
925 ℃ of degree design temperature=902 ℃ actual temperatures; With
1130 ℃ of programming temperature=1104 ℃ actual temperatures.
Carrier L (the present invention) is prepared as follows.The 120g consumption is purchased the γ alumina (by LaRocheIndustries Inc., Atlanta, Georgia provides, and obtains as the precalcining sheet stock form with about 1/8 inch diameter) under 120 ℃ temperature, in drying oven, place about 15 minutes time.The γ alumina that heated is used the calcium nitrate tetrahydrate (Ca (NO of about 50g then 3) 24H 2O) dipping, it melted about 15 minutes in drying oven under about 120 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch) after the deionized water that adds 25g.By using the 5mL pipette, the calcium nitrate tetrahydrate of fusing was added drop-wise to through 30 minutes carries out the dip operation of γ alumina sheet stock in the γ alumina pellet with the fusing calcium nitrate tetrahydrate.In the interpolation process of fusing calcium nitrate tetrahydrate, continuous stirring γ alumina pellet.When finishing, the alumina that combines calcium is put into drying oven and heated a whole night (about 16 hours) at 120 ℃ times.
The so dry alumina of crossing in conjunction with calcium is put into quartzy calcining tube then, is heated to 210 ℃ and 210 ℃ of a period of times that keep 3 hours down.This temperature is enhanced 320 ℃ and 320 ℃ of a period of times that keep down 3 hours then.This temperature is enhanced 360 ℃ and 360 ℃ of times that keep down 3 hours then.This temperature is enhanced 400 ℃ and 400 ℃ of times that keep down 14.5 hours then.This temperature is enhanced 500 ℃ and 500 ℃ of times that keep 2 hours then.This temperature is enhanced 600 ℃ and 600 ℃ of times that keep 0.5 hour then.Do not observe the release of NOx gas.Allow calcining tube be cooled to room temperature (promptly about 20 ℃ to about 25 ℃) then.Alumina in conjunction with calcium is transferred to porcelain crucible then, with the same Programmed Temperature Ramp cited for carrier K of the present invention under the temperature that raises.After this ProgrammedTemperature Ramp heating, allow porcelain crucible cool off about 2 hours time, the calcium aluminate catalyst carrier is provided.
Carrier M (the present invention) is prepared as follows.The γ alumina (by UOPInc., McCook, Illinois provides, and obtains as the precalcining sheet stock form with about 1/8 inch diameter) that is purchased of 100g consumption is placed about 15 minutes time in drying oven under 120 ℃ temperature.The γ alumina that heated is used the calcium nitrate tetrahydrate (Ca (NO of about 60g then 3) 24H 2O) dipping, it melted about 15 minutes in drying oven under about 120 ℃ temperature under the pressure of about atmospheric pressure (promptly about 14.7 pounds/square inch) after the deionized water that adds 20g.By using the 5mL pipette, the fusing calcium nitrate tetrahydrate was added drop-wise to through 30 minutes carries out the dip operation of γ alumina sheet stock in the γ alumina sheet stock with the fusing calcium nitrate tetrahydrate.In the interpolation process of fusing calcium nitrate tetrahydrate, continuous stirring γ alumina sheet stock.When finishing, the alumina that combines calcium is put into drying oven and descended heating 3 hours at 120 ℃.
The so dry alumina of crossing in conjunction with calcium is put into quartzy calcining tube then, is heated to 120 ℃ and keeps 3 hours.This temperature is enhanced 220 ℃ and 220 ℃ of times that keep down 3 hours then.This temperature is enhanced 330 ℃ and 330 ℃ of times that keep 15 hours then.This temperature is enhanced 400 ℃ and 400 ℃ of times that keep down 3 hours then.This temperature is enhanced 500 ℃ and 500 ℃ of times that keep 2 hours then.This temperature is enhanced 600 ℃ and keep about 1 hour a period of times down at 600 ℃ then.Under 600 ℃, do not observe the release of NOx gas.Allow calcining tube be cooled to room temperature (promptly about 20 ℃ to about 25 ℃) then.Alumina in conjunction with calcium is transferred to porcelain crucible then, with narration for carrier K of the present invention in the temperature that raises under the cited same ProgrammedTemperature Ramp.After this Programmed Temperature Ramp heating, allow porcelain crucible cool off about 2 hours time, the calcium aluminate catalyst carrier is provided.
Carrier J (contrast) be according to in the preparation of the described same procedure of example I.
From the physical characteristic of analyzing, as carrier J, K, the surface area of L and M, pore volume is in average pore size and the crystal farmland size column Table II below." crystal farmland size " is to measure from the spectral line broadening of X-ray diffraction spectral line.In addition, this X-ray diffraction spectral line confirms that carrier J has zinc aluminate structure, and carrier K has magnesium aluminate structure and carrier L and M and respectively has the calcium aluminate structure.
Table II
Carrier Calcining heat (℃) Surface area (m2/g) Pore volume (mL/g) Average pore size (ang.) Metal aluminate CDS (ang.) α-Al 2O 3CDS(ang.) δ-Al 2O 3CDS(ang.) θ-Al 2O 3CDS(ang.) γ-Al 2O 3CDS(ang.)
K (the present invention) (MgOAl 2O 3) 1100 78 0.136 692 580 190 ND ND ND
L (the present invention) (CaOAl 2O 3) 1100 74 0.143 781 ND* ND ND ND ND
M (the present invention) (CaOAl 2O 3) 1100 11 0.129 468 405 535 60 ND ND
J (the present invention) (ZnOAl 2O 3) 1100 (steam) 53 0.533 395 100 ＞2000 150 300 ND
CDS=crystal farmland size ang.=dust ND=undetermined *=X-ray diffraction spectral line confirms that carrier L has the calcium aluminate structure
Data declaration in the Table II, the inventive method described here can be used in produces metal aluminate catalyst support such as magnesium aluminate catalyst carrier or calcium aluminate catalyst carrier.

Claims (46)

1. produce the method for metal aluminate catalyst support, comprising:
(a) in alumina in conjunction with the deposite metal component, provide in conjunction with the alumina of metal and
(b) under calcination condition, calcine this and obtain metal aluminate catalyst support in conjunction with the alumina of metal, wherein calcination condition is included in about 600 ℃ of temperature to about 1350 ℃ of scopes, pressure in about 48kPa arrives about 5167kPa (about 7 absolute per square inch poundages (pound/square inch) are to about 750 pounds/square inch) scope, and the time between about 1 hour to about 60 hours; With
In addition, wherein this deposite metal component comprises molten metal component under melting condition.
2. flood this alumina according to the process of claim 1 wherein that this integrating step (a) comprises with the deposite metal component.
3. according to the method for claim 2, wherein this melting condition comprises:
Be lower than the temperature of the decomposition temperature of metal component,
Time between about 1 minute to about 2 hours and
At the pressure of about atmospheric pressure to about 1033kPa (about 150 pounds/square inch) scope.
4. according to the method for claim 3, wherein this dipping comprises the deposite metal component is poured on the surface of alumina the deposite metal component is joined in the alumina, thereby has obtained a kind of alumina in conjunction with metal that whole basically surface area of alumina has wherein applied the deposite metal component.
5. according to the method for claim 4, wherein this deposite metal component is poured onto on the surface of alumina, and meanwhile alumina is under the constant stirring or rollover states.
6. according to the method for claim 5, wherein this metal component is to be selected from the zinc component, magnesium component, calcium component, barium component, beryllium component, cobalt component, iron component, manganese component, strontium component, lithium component, potassium component and their bond.
7. according to the method for claim 1, wherein the amount in conjunction with the metal component in this alumina is enough to obtain metal aluminate catalyst support, and the latter has generally and to arrive metal aluminate amount between about 100wt% based on the metal aluminate catalyst support gross weight at about 1wt%.
8. according to the process of claim 1 wherein that this metal component is to be selected from the zinc component, magnesium component, calcium component, barium component, beryllium component, cobalt component, iron component, manganese component, strontium component, lithium component, potassium component and their bond.
9. method according to Claim 8, wherein this zinc component is to be selected from zinc nitrate hexahydrate, zinc nitrate, the zinc nitrate of hydration, zinc chloride, zinc acetate dihydrate, zinc acetylacetone,2,4-pentanedione salt hydrate, zinc carbonate hydroxide monohydrate, the zinc perchlorate hexahydrate, the zinc sulfate of hydration, zinc sulfate monohydrate, zinc sulfate heptahydrate and their bond.
10. method according to Claim 8, wherein this magnesium component is to be selected from magnesium nitrate hexahydrate, magnesium nitrate, the magnesium nitrate of hydration, magnesium chloride, the magnesium chloride of hydration, magnesium chloride hexahydrate, magnesium acetate 4 hydrate, magnesium acetylacetonate dihydrate, the Marinco C pentahydrate, magnesium perchlorate, magnesium perchlorate hexahydrate, magnesium sulfate, magnesium sulfate 7 hydrate, magnesium sulfate monohydrate and their bond.
11. method according to Claim 8, wherein this calcium component is to be selected from calcium nitrate tetrahydrate, calcium nitrate, the calcium nitrate of hydration, calcium chloride, the calcium chloride of hydration, calcium chloride dihydrate, calcium chloride hexahydrate, calcium chloride hydrate, the calcium acetate hydrate, calcium acetate monohydrate, calcium acetylacetone,2,4-pentanedione salt hydrate, the Calcium perchlorate tetrahydrate, calcium sulfate, calcium sulfate dihydrate, calcium sulfate hemihydrate and their bond.
12. method according to Claim 8, wherein this barium component is to be selected from barium nitrate, the barium nitrate of hydration, barium chloride, the barium chloride of hydration, barium chloride dihydrate, barium acetate, barium acetylacetone,2,4-pentanedione salt hydrate, brium carbonate, barium perchlorate, barium perchlorate trihydrate, barium sulfate and their bond.
13. method according to Claim 8, wherein this beryllium component is to be selected from the beryllium nitrate trihydrate, the beryllium nitrate of hydration, beryllium chloride, the beryllium sulfate of hydration, beryllium sulfate tetrahydrate and their bond.
14. method according to Claim 8, wherein this cobalt component is to be selected from Cobalt(II) nitrate hexahydrate, the cobalt nitrate of hydration, cobalt chloride, the cobalt chloride of hydration, cobalt chloride hexahydrate, the cobalt chloride hydrate, cobalt acetate tetrahydrate, cobalt acetylacetonate, cobalt acetylacetone,2,4-pentanedione salt hydrate, the cobalt carbonate hydrate, cobaltous perchlorate hexahydrate, the cobaltous sulfate of hydration, cobaltous sulfate hydrate and their bond.
15. method according to Claim 8, wherein this iron component is to be selected from the ferric nitrate nonahydrate, the ferric nitrate of hydration, iron chloride, the iron chloride of hydration, iron chloride tetrahydrate, ferric chloride hexahydrate, ferric acetate, the iron acetylacetonate, ferric perchlorate's hexahydrate, the ferric sulfate of hydration, ferric sulfate heptahydrate and their bond.
16. method according to Claim 8, wherein this manganese component is to be selected from the manganese nitrate hexahydrate, the manganese nitrate of hydration, the manganese nitrate hydrate, manganese chloride, the manganese chloride of hydration, the manganese chloride tetrahydrate, manganese acetate dihydrate, manganese acetate tetrahydrate, the manganese acetylacetonate, manganese carbonate, perchloric acid manganese hexahydrate, the manganese sulfate of hydration, manganese sulfate monohydrate and their bond.
17. method according to Claim 8, wherein this strontium component is to be selected from strontium nitrate, the strontium nitrate of hydration, strontium chloride, the strontium chloride of hydration, the strontium chloride hexahydrate, strontium acetate, strontium acetylacetonate, strontium carbonate, perchloric acid strontium hydrate, the strontium sulfate of hydration, strontium sulfate and their bond.
18. method according to Claim 8, wherein this lithium component is to be selected from lithium nitrate, the lithium nitrate of hydration, lithium chloride, the lithium chloride of hydration, lithium chloride hydrate, lithium acetate dihydrate, the lithium acetylacetonate, lithium perchlorate, lithium perchlorate trihydrate, lithium sulfate, lithium sulfate monohydrate and their bond.
19. method according to Claim 8, wherein this potassium component is to be selected from potassium nitrate, the potassium nitrate of hydration, potassium chloride, the potassium chloride of hydration, potassium acetylacetonate hemihydrate, potash sesquialter hydrate, potassium hyperchlorate, potassium sulfate and their bond.
20. according to the method for claim 3, wherein the temperature of melting condition is to arrive in about 160 ℃ of scopes at about 25 ℃.
21. according to the process of claim 1 wherein that this carries out drying in conjunction with the alumina of metal before carrying out calcining step (b) under drying condition.
22. according to the method for claim 21, wherein this drying condition comprises:
In about 80 ℃ of temperature that arrive in about 140 ℃ of scopes,
Time between about 0.5 hour to about 60 hours and
At the pressure of about atmospheric pressure to about 1033kPa (about 150 pounds/square inch) scope.
23. according to the process of claim 1 wherein in integrating step (a) alumina in alumina in conjunction with metal component before by allow alumina experience heating condition heat and wherein this heating condition comprise:
In about 80 ℃ of temperature that arrive in about 150 ℃ of scopes,
Time between about 1 minute to about 2 hours and
At the pressure of about atmospheric pressure to about 1033kPa (about 150 pounds/square inch) scope.
24. according to the process of claim 1 wherein afterwards at calcining step (b), on the outer surface of alumina, or on the surface of alumina, but be not limited to form metal aluminate on these surfaces.
25. according to the process of claim 1 wherein the amount of metal aluminate of metal aluminate catalyst support be based on about 1wt% of metal aluminate catalyst support gross weight in about 100wt% scope.
26. according to the method for claim 25, wherein the amount of the α alumina of metal aluminate catalyst support is to arrive in about 99wt% scope at the about 0wt% based on the metal aluminate catalyst support gross weight.
27. according to the method for claim 26, wherein the amount of the γ alumina of metal aluminate catalyst support is to arrive in about 60wt% scope at the about 0wt% based on the metal aluminate catalyst support gross weight.
28. according to the method for claim 27, wherein the surface area of metal aluminate catalyst support is at about 1m 2/ g is to about 200m 2In/g the scope.
29. according to the method for claim 28, wherein the pore volume of metal aluminate catalyst support is in about 0.05ml/g arrives about 2ml/g scope.
30. according to the method for claim 29, wherein the average pore size of metal aluminate catalyst support is in about 50 dusts arrive about 1000 dust scopes.
31. according to the method for claim 30, wherein the crystal farmland size of the metal aluminate of metal aluminate catalyst support is in about 25 dusts arrive about 1750 dust scopes.
32. according to the method for claim 31, wherein the α alumina of metal aluminate catalyst support has in the crystal farmland size of about 25 dusts to about 3000 dust scopes.
33. according to the process of claim 1 wherein that the alumina in integrating step (a) is to be selected from the α alumina, β alumina, δ alumina, η alumina, γ alumina and their bond.
34. according to the method for claim 33, wherein the alumina in integrating step (a) is a sheet stock, pellet, extrudate, the form of ball and their bond.
35. according to the method for claim 34, wherein the alumina in integrating step (a) has at about 5m 2/ g is to about 400m 2Surface area between the/g; At the pore volume of about 0.05ml/g between about 2ml/g; In the average pore size of about 5 dusts between about 600 dusts; With in the granularity of about 0.5mm between about 10mm.
36. produce the method for metal aluminate catalyst support, comprising:
(a) flood alumina with metal component, thus obtain in conjunction with the alumina of metal and
(b) under calcination condition, calcine this and obtain metal aluminate catalyst support in conjunction with the alumina of metal, wherein calcination condition is included in about 600 ℃ of temperature to about 1350 ℃ of scopes, pressure in about 48kPa arrives about 5167kPa (about 7 absolute per square inch poundages (pound/square inch) are to about 750 pounds/square inch) scope, and the time between about 1 hour to about 60 hours; With
In addition, wherein this metal component is to exist with aqueous solution form, and this solution is formed by metal component being dissolved in the solvent that is selected from water, alcohol, ester, ether, ketone and their bond; With this metal component is to be selected from the zinc component, magnesium component, calcium component, barium component, beryllium component, cobalt component, iron component, manganese component, strontium component, lithium component, potassium component and their bond.
37. according to the method for claim 36, wherein this zinc component is the zinc nitrate hexahydrate; This magnesium component is the magnesium nitrate hexahydrate; This calcium component is a calcium nitrate tetrahydrate; This barium component is a barium nitrate; This beryllium component is the beryllium nitrate trihydrate; This cobalt component is a Cobalt(II) nitrate hexahydrate; This iron component is the ferric nitrate nonahydrate; This manganese component is the manganese nitrate hexahydrate; This strontium component is a strontium nitrate; This lithium component is a lithium nitrate; With this potassium component be potassium nitrate.
38. according to the method for claim 37, wherein the amount of the metal aluminate of metal aluminate catalyst support is to arrive in about 100wt% scope at the about 1wt% based on the metal aluminate catalyst support gross weight; The amount of the α alumina of metal aluminate catalyst support is to arrive in about 99wt% scope at the about 0wt% based on the metal aluminate catalyst support gross weight; With the amount of the γ alumina of metal aluminate catalyst support be based on about 0wt% of metal aluminate catalyst support gross weight in about 60wt% scope.
39. composition by the method preparation of any one among the aforementioned claim 1-38.
40. comprise the metal aluminate catalyst support of metal aluminate and alumina, wherein alumina is selected from the α alumina, β alumina, δ alumina, η alumina, γ alumina and their bond.
41. according to the metal aluminate catalyst support of claim 40, wherein the amount of the metal aluminate of metal aluminate catalyst support is to arrive in about 100wt% scope at the about 1wt% based on the metal aluminate catalyst support gross weight.
42. according to the metal aluminate catalyst support of claim 41, wherein the amount of the α alumina of metal aluminate catalyst support is to arrive in about 99wt% scope at the about 0wt% based on the metal aluminate catalyst support gross weight.
43. according to the metal aluminate catalyst support of claim 42, wherein the amount of the γ alumina of metal aluminate catalyst support is to arrive in about 60wt% scope at the about 0wt% based on the metal aluminate catalyst support gross weight.
44. according to the metal aluminate catalyst support of claim 43, wherein this metal aluminate is to be selected from zinc aluminate, magnesium aluminate, calcium aluminate, barium aluminate, beryllium aluminate, cobalt aluminate, iron aluminate could, manganese aluminate, strontium aluminate, lithium aluminate, potassium aluminate and their bond.
45. according to the metal aluminate catalyst support of claim 44, wherein the surface area of metal aluminate catalyst support is at about 1m 2/ g is to about 200m 2In/g the scope, the pore volume of metal aluminate catalyst support is in about 0.05ml/g arrives about 2ml/g scope, the average pore size of metal aluminate catalyst support is in about 50 dusts arrive about 1000 dust scopes, and the crystal farmland size of the metal aluminate of metal aluminate catalyst support is in about 25 dusts arrive about 1750 dust scopes.
46. according to the metal aluminate catalyst support of claim 45, wherein the α alumina of metal aluminate catalyst support has in the crystal farmland size of about 25 dusts to about 3000 dust scopes.
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